CN102530910B - Method for preparing fluorinated graphene - Google Patents
Method for preparing fluorinated graphene Download PDFInfo
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- CN102530910B CN102530910B CN201010600423.9A CN201010600423A CN102530910B CN 102530910 B CN102530910 B CN 102530910B CN 201010600423 A CN201010600423 A CN 201010600423A CN 102530910 B CN102530910 B CN 102530910B
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Abstract
The invention discloses a method for preparing fluorinated graphene, which comprises the following steps: providing graphite; preparing graphene oxide by using the graphite; reducing the graphene oxide by a liquid phase to obtain graphene; and reacting the graphene with a fluorine-containing matter to obtain fluorinated graphene. The fluorinated graphene is obtained by reacting the graphene with the fluorine-containing matter, particularly a fluorine-containing gas or fluorine-containing compound. The preparation method has fewer steps, adopts simple process and has a good application prospect.
Description
[technical field]
The invention belongs to organic semiconductor material technical field, be specifically related to the preparation method of fluorinated graphene.
[background technology]
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Graphene is called " nova " that is rising in Materials science and Condensed Matter Physics field, many novelties that it has and unique character and potential application are just attracting many scientific workers.Single-layer graphene has large specific surface area, good conduction, heat conductivility and low thermal expansivity.As: 1. high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm2/V*s); 4. high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.
Fluorographite is as the active substance of high-performance lithium ion battery, and oneself causes mechanism of new electrochemical power sources investigators' very big interest and attention, and has succeeded in developing corresponding high tension battery.Fluorographite-lithium cell has the performance of following excellence: (1) voltage is high, energy density is high.The actual nominal voltage of general manganese cell is 3V, and energy density is 360wh/kg, and the nominal voltage of cylindrical fluorographite-lithium cell is two times of manganese cell, and energy density is 5～10 times of manganese cell.(2) utilization ratio is high, voltage is steady.According to exoelectrical reaction, owing to generating the carbon of electroconductibility, utilization ratio is almost 100%, and when electric discharge, internal resistance does not increase, and sparking voltage is stabilized to the latter stage of discharging.Shelf lives is long, Applicable temperature scope is wide.
Fluorinated graphene is that a kind of physical strength is high, chemistry and the stable compound of thermal property.The very similar tetrafluoroethylene of this novel material performance, is referred to as two-dimentional tetrafluoroethylene conventionally.
But how obtaining easily fluorinated graphene is a current difficult problem.
[summary of the invention]
Based on this, be necessary to provide the preparation method of the simple fluorinated graphene of a kind of technique
A kind of method of fluorinated graphene comprises the steps:
Graphite is provided;
Use described graphite-made for graphene oxide;
Described in liquid-phase reduction, graphene oxide makes Graphene;
Graphene reacts and makes fluorinated graphene with fluorine-containing material.
Preferably, described Graphene reacts with fluorine-containing material for described Graphene and by N
2and F
2the mixed gas of composition is 50～500 DEG C in temperature, makes described fluorinated graphene under the condition that the reaction times is 3～120h.
Preferably, F in described mixed gas
2volume fraction be 10%～30%.
Preferably, F in described mixed gas
2volume fraction be 20%.
Preferably, use described graphite-made to comprise for the step of graphene oxide:
Described graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES are joined according to mass ratio 2:1:1 in the vitriol oil of 75～95 DEG C, naturally cooling after stirring, washing, to dry after neutral, obtains pretreated mixture;
Described pretreated mixture and potassium permanganate are joined to temperature lower than in the vitriol oil of 20 DEG C, and then oil bath 1.5～2.5h at 30～40 DEG C, adds deionized water, adds hydrogen peroxide reaction after 15min, suction filtration, collection solid;
Described solid washs with dilute hydrochloric acid, dry, obtains described graphene oxide.
Preferably, the step that described in liquid-phase reduction, graphene oxide makes Graphene comprises:
Described graphene oxide is mixed with deionized water and be dispersed into suspension liquid;
In described suspension liquid, add reductive agent, 90～100 DEG C of thermal reduction 24～28h obtain Graphene suspension liquid;
After filtering, described Graphene suspension liquid collects filter residue, and dry after water, methanol wash successively, obtain described Graphene.
Preferably, described reductive agent is hydrazine hydrate.
Preferably, it is cooling after described Graphene and fluorochemicals are processed 1～10h taking mass ratio as 1:1～1:100 at 200～1000 DEG C that described Graphene reacts with fluorine-containing material, and water and washing with alcohol, dry, obtain described fluorinated graphene successively.
Preferably, described fluorochemicals is at least one in Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and Sodium Silicofluoride.
Preferably, described fluorochemicals is at least one in tetrafluoroethylene, polyhexafluoropropylene and polyvinylidene difluoride (PVDF).
The preparation method of above-mentioned fluorinated graphene uses graphite-made for graphene oxide, then liquid-phase reduction graphene oxide obtains Graphene, finally utilizes Graphene and N
2and F
2mixed gas or the fluorochemicals of composition react at a certain temperature, prepare fluorinated graphene, and this preparation method's step is few, technique is simple, has stronger application prospect.
[brief description of the drawings]
Fig. 1 is the preparation method's of the fluorinated graphene of an embodiment schema;
Fig. 2 is the preparation method's of the fluorinated graphene of another embodiment schema;
Fig. 3 is the XPS collection of illustrative plates of the C1s of the fluorinated graphene prepared of embodiment mono-;
Fig. 4 is the XPS collection of illustrative plates of the F1s of the fluorinated graphene prepared of embodiment mono-;
Fig. 5 is the SEM Electronic Speculum picture of the fluorinated graphene prepared of embodiment mono-.
[embodiment]
Below in conjunction with drawings and Examples, the preparation method of fluorinated graphene is further explained to explanation.
A kind of fluorinated graphene, wherein, the mass percent of F is 0.5<F%<30%, the shared mass percent of C is 70%<C%<99.5%.
This fluorinated graphene is made by Graphene generation fluoro-reaction.
Under Electronic Speculum, can find out, this fluorinated graphene surface has fold-like structures that can increasing specific surface area.
A kind of preparation method of above-mentioned fluorinated graphene as shown in Figure 1, comprises the steps:
S110, provide graphite
Buy purity and exceed 99.5% graphite.
S120, use graphite-made are for graphene oxide
General, can be by Hummers legal system for graphite oxide, be placed in same container water-bath or oil bath heating by graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid), until fully taking out after oxidation, first reduce potassium permanganate with hydrogen peroxide, with distilled water or hydrochloric acid washed product several, after being dried, obtain graphite oxide.
In order to prepare graphene oxide, can carry out some to Hummers method and improve, the preparation process after improvement comprises the steps.
First, by graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2:1:1 join 75～95 DEG C the vitriol oil in, naturally cooling after stirring, washing, to dry after neutral, obtains pretreated mixture.
Secondly, described pretreated mixture and potassium permanganate are joined in the vitriol oil, keep temperature lower than 20 DEG C, 30～40 DEG C of oil bath 1.5～2.5h, add deionized water afterwards, add hydrogen peroxide reaction after 15min, suction filtration, collection solid.
Finally, above-mentioned solid is washed with dilute hydrochloric acid, dry, obtain graphene oxide.
The object of oil bath is in order better to control temperature of reaction, in other embodiment, also can to adopt water-bath.
S130, liquid-phase reduction graphene oxide make Graphene
First the graphene oxide, S120 being obtained mixes with deionized water and is dispersed into suspension liquid.Generally can adopt ultrasonic echography to disperse graphene oxide.
Secondly, in above-mentioned suspension liquid, add reductive agent, be heated to 90～100 DEG C and carry out thermal reduction, after 24～28h, obtain Graphene suspension liquid.Reductive agent adopts has the soluble compound of certain thermostability, and general can enumerate: hydrazine hydrate, sodium borohydride and to benzene two ammoniums, be preferably hydrazine hydrate.
Finally, after being filtered, Graphene suspension liquid collects filter residue, and dry after water, methanol wash successively, obtain Graphene.
S140, Graphene react and obtain fluorinated graphene with fluorine simple substance
The Graphene being dried and the fluorine simple substance (F that utilize S130 step to obtain
2) react and prepare fluorinated graphene, this method is called vapor phase process, adopts N
2and F
2mixed gas, concrete steps are as follows:
The Graphene that S130 step is obtained is put into reactor, passes into dry nitrogen 0.5～4h, then passes into N
2and F
2mixed gas (F
2volume fraction be 10%～30%), holding temperature is 50～500 DEG C, reaction 3～120h, obtain fluorinated graphene.
By test of many times, find F
2volume fraction gets 20%, temperature of reaction is got 250 DEG C, reaction times to get 6h be optimum reaction condition.
The another kind of preparation method of above-mentioned fluorinated graphene as shown in Figure 2, comprises the steps:
S210, provide graphite
Buy purity and exceed 99.5% graphite.
S220, use graphite-made are for graphene oxide
General, can be by Hummers legal system for graphite oxide, be placed in same container water-bath or oil bath heating by graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid), until fully taking out after oxidation, first reduce potassium permanganate with hydrogen peroxide, with distilled water or hydrochloric acid washed product several, after being dried, obtain graphite oxide.
In order to prepare graphene oxide, can carry out some to Hummers method and improve, the preparation process after improvement comprises the steps.
First, by graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2:1:1 join 75～95 DEG C the vitriol oil in, naturally cooling after stirring, washing, to dry after neutral, obtains pretreated mixture.
Secondly, described pretreated mixture and potassium permanganate are joined in the vitriol oil, keep temperature lower than 20 DEG C, 30～40 DEG C of oil bath 1.5～2.5h, add deionized water afterwards, add hydrogen peroxide reaction after 15min, suction filtration, collection solid.
Finally, above-mentioned solid is washed with dilute hydrochloric acid, dry, obtain graphene oxide.
The object of oil bath is in order better to control temperature of reaction, in other embodiment, also can to adopt water-bath.
S230, liquid-phase reduction graphene oxide make Graphene
First the graphene oxide, S220 being obtained mixes with deionized water and is dispersed into suspension liquid.Generally can adopt ultrasonic echography to disperse graphene oxide.
Secondly, in above-mentioned suspension liquid, add reductive agent, be heated to 90～100 DEG C and carry out thermal reduction, after 24～28h, obtain Graphene suspension liquid.Reductive agent adopts has the soluble compound of certain thermostability, and general can enumerate: hydrazine hydrate, sodium borohydride and to benzene two ammoniums, be preferably hydrazine hydrate.
Finally, after being filtered, Graphene suspension liquid collects filter residue, and dry after water, methanol wash successively, obtain Graphene.
S240, Graphene react and obtain fluorinated graphene with fluorochemicals
Utilize the Graphene being dried that S230 step obtains to react and prepare fluorinated graphene with fluorochemicals, this method is called solid phase method, be divided into fluorine-containing inorganics and fluoropolymer according to fluorochemicals, solid phase method comprises again inorganic solid phase method and Organic Solid-Phase method, specifically introduces one by one below.
Inorganic solid phase method is prepared fluorinated graphene
Present method adopts the Graphene being dried that obtains with S230 step of heat decomposable fluorine-containing inorganics to react, and what the fluorine-containing inorganics of employing was general can enumerate as Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and Sodium Silicofluoride.When actually operating, can select wherein one, also can select multiple mixing.
First, fluorine-containing inorganics is carried out to drying treatment, drying temperature is lower than its decomposition temperature.
Then, after Graphene and fluorine-containing inorganics being mixed for 1:1～1:100, pack reactor according to Graphene and fluorine-containing inorganics quality into, 200～1000 DEG C of thermal treatment 1～10h, fully cooling after reaction, after taking-up reactant successively water and washing with alcohol, 80 DEG C of vacuum-drying 24h obtain fluorinated graphene.
Thermal treatment actual temp is determined according to the fluorine-containing inorganics of actual selection.
Organic Solid-Phase legal system is for fluorinated graphene
The Graphene being dried that present method adopts heat decomposable fluoropolymer to obtain with S230 step reacts, and what the fluoropolymer of employing was general can enumerate as tetrafluoroethylene, polyhexafluoropropylene and polyvinylidene difluoride (PVDF).When actually operating, can select wherein one, also can select multiple mixing.
First, more than fluoropolymer is boiled to 3h in boiling water, then dry.
Then, be that Graphene and fluoropolymer in organic solvent, are mixed post-drying by 1:1～1:100 according to Graphene and fluoropolymer mass ratio, after compressing tablet under oxygen free condition 200～800 DEG C of thermal treatment 1～10h, fully cooling after reaction, obtain fluorinated graphene.
General, oxygen free condition can be realized by rare gas element or nitrogen protection.
The preparation method of above-mentioned fluorinated graphene uses graphite-made for graphene oxide, then liquid-phase reduction graphene oxide obtains Graphene, finally recycles Graphene and N
2and F
2mixed gas or the fluorochemicals of composition react at a certain temperature, prepare fluorinated graphene.This preparation method's step is few, technique is simple, has stronger application prospect.
The fluorinated graphene preparing can be applied the electrode materials as ultracapacitor, lithium-ion secondary cell.
It is below specific embodiment part.
Embodiment 1
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) graphene oxide: by improved Hummers legal system for graphene oxide.Its concrete steps are that 20g50 order Graphite Powder 99,10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 DEG C, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 DEG C, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 DEG C, then in the oil bath of 35 DEG C, keep after 1.5h, slowly add 920mL deionized water.After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 DEG C of vacuum-drying 48h with the hydrochloric acid that 5L concentration is 10%.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Finally add wherein hydrazine hydrate (1mL, 98%) and be heated to 100 DEG C of reaction 36h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, dry 48h in vacuum drying oven at 80 DEG C.
(4) fluorinated graphene: in (3) gained Graphene by with F
2reaction obtains fluorinated graphene.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 2h, then pass into that fluorine gas accounts for 20% fluorine gas and the mixed gas of nitrogen reacts 60h with Graphene at 250 DEG C, can obtain fluorinated graphene.
Gained fluorinated graphene is carried out to following experiment:
XPS test experiments condition: sample is analyzed with VG Scientific ESCALab220i-XL type photoelectron spectrograph.Excitaton source is Al K α X ray, the about 300W of power.Base vacuum when analysis is 3 × 10
-9mbar.Electron binding energy is proofreaied and correct with the C1s peak (284.8eV) that pollutes carbon.
Element relative quantification calculates:
Relative atom per-cent
In formula: I
ithe peak intensity (area) of-i element
S
ithe relative elemental sensitivity factor of-i element
Can show that by table 1 mass percent of F is 30%.
The XPS collection of illustrative plates of the C1s of fluorinated graphene prepared by the present embodiment as shown in Figure 3, as can be seen from the figure, the fluorinated graphene making has very strong peak value at 284.8eV place, in corresponding fluorinated graphene, carbon bond structure is C – C(284.8eV).
The XPS collection of illustrative plates of the F1s of fluorinated graphene prepared by the present embodiment as shown in Figure 4, as can be seen from the figure, the fluorinated graphene making has very strong peak value at 689.5eV place, in corresponding fluorinated graphene, carbon bond structure is C – F(689.5eV).
The SEM Electronic Speculum picture of fluorinated graphene prepared by the present embodiment as shown in Figure 5, as can be seen from the figure, the fluorinated graphene surface making has wrinkle accordion structure, and this wrinkle accordion structure is conducive to improve the specific surface area of material.
Embodiment 2
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3), gained Graphene is by reacting and obtain fluorinated graphene with F2.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 4h, then pass into that fluorine gas accounts for 15% fluorine gas and the mixed gas of nitrogen reacts 6h with Graphene at 250 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 28.6%.
Embodiment 3
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3) gained Graphene by with F
2reaction obtains fluorinated graphene.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 0.5h, then pass into that fluorine gas accounts for 10% fluorine gas and the mixed gas of nitrogen reacts 3h with Graphene at 500 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 18.4%.
Embodiment 4
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3), gained Graphene is by reacting and obtain fluorinated graphene with F2.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 2h, then pass into that fluorine gas accounts for 30% fluorine gas and the mixed gas of nitrogen reacts 50h with Graphene at 200 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 25.2%.
Embodiment 5
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3) gained Graphene by with F
2reaction obtains fluorinated graphene.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 2h, then pass into that fluorine gas accounts for 15% fluorine gas and the mixed gas of nitrogen reacts 120h with Graphene at 150 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 7.5%.
Embodiment 6
Graphite → graphene oxide → Graphene → fluorinated graphene
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3) gained Graphene by with F
2reaction obtains fluorinated graphene.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 2h, then pass into that fluorine gas accounts for 25% fluorine gas and the mixed gas of nitrogen reacts 100h with Graphene at 100 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 0.5%.
Embodiment 7
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 1.
(3) prepare Graphene as described in Example 1.
(4) fluorinated graphene: in (3) gained Graphene by with F
2reaction obtains fluorinated graphene.Its concrete steps are that dried Graphene is packed in reactor and passes into dry nitrogen 2h, then pass into that fluorine gas accounts for 18% fluorine gas and the mixed gas of nitrogen reacts 30h with Graphene at 50 DEG C, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 21%.
Embodiment 8
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) graphene oxide: by improved Hummers legal system for graphene oxide.Its concrete steps are that 20g50 order Graphite Powder 99,10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 95 DEG C, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 DEG C, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 DEG C, then in the oil bath of 40 DEG C, keep after 1.5h, slowly add 920mL deionized water.After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 DEG C of vacuum-drying 48h with the hydrochloric acid that 5L concentration is 10%.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Finally add wherein hydrazine hydrate (1mL, 98%) and be heated to 90 DEG C of reaction 48h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, dry 48h in vacuum drying oven at 80 DEG C.
(4) fluorinated graphene: prepare fluorinated graphene by solid phase method.Its concrete steps are Sodium tetrafluoroborate and pass through fully dry Graphene according to certain mass ratio, potassium fluoborate: Graphene=1:1 packs in reactor after mixing and weighing, set temperature of reaction according to the decomposition temperature of inorganic fluorine source, at 1000 DEG C, react 1h.Cooling a little rear taking-up reactant, after water and washing with alcohol, obtains fluorinated graphene at 80 DEG C of vacuum-drying 24h successively.
Can show that by table 1 mass percent of F is 15%.
Embodiment 9
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) graphene oxide: by improved Hummers legal system for graphene oxide.Its concrete steps are that 20g50 order Graphite Powder 99,10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 75 DEG C, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 DEG C, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 DEG C, then in the oil bath of 30 DEG C, keep after 2.5h, slowly add 920mL deionized water.After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 DEG C of vacuum-drying 48h with the hydrochloric acid that 5L concentration is 10%.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Finally add wherein hydrazine hydrate (1mL, 98%) and be heated to 100 DEG C of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, dry 48h in vacuum drying oven at 80 DEG C.
(4) fluorinated graphene: prepare fluorinated graphene by solid phase method.Its concrete steps are Neutral ammonium fluoride and pass through fully dry Graphene according to certain mass ratio, Neutral ammonium fluoride: Graphene=100:1 packs in reactor after mixing and weighing, set temperature of reaction according to the decomposition temperature of inorganic fluorine source, at 200 DEG C, react 10h.Cooling a little rear taking-up reactant, after water and washing with alcohol, obtains fluorinated graphene at 80 DEG C of vacuum-drying 24h successively.
Can show that by table 1 mass percent of F is 23%.
Embodiment 10
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) graphene oxide: by improved Hummers legal system for graphene oxide.Its concrete steps are that 20g50 order Graphite Powder 99,10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 DEG C, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 DEG C, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 DEG C, then in the oil bath of 35 DEG C, keep after 2h, slowly add 920mL deionized water.After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 DEG C of vacuum-drying 48h with the hydrochloric acid that 5L concentration is 10%.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Finally add wherein hydrazine hydrate (1mL, 98%) and be heated to 100 DEG C of reaction 36h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, dry 48h in vacuum drying oven at 80 DEG C.
(4) fluorinated graphene: prepare fluorinated graphene by solid phase method.Its concrete steps are: process is boiled to 3h in boiling water, fluoropolymer tetrafluoroethylene after oven dry according to a certain percentage (tetrafluoroethylene: Graphene=1:1) mixes in organic solvent, then put into baking oven about 150 DEG C oven dry, and then compressing tablet is put into nickel boat.Nickel boat is put into silica tube the appropriate rear heated sealed of logical nitrogen of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature, at 1000 DEG C, after reaction 1h, is taken out silica tube cooling, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 2.8%.
Embodiment 11
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 10.
(3) prepare Graphene as described in Example 10.
(4) fluorinated graphene: prepare fluorinated graphene by solid phase method.Its concrete steps are: process is boiled to 3h in boiling water, polyhexafluoropropylene after oven dry according to a certain percentage (polyhexafluoropropylene: Graphene=100:1) mixes in organic solvent, then put into baking oven about 150 DEG C oven dry, and then compressing tablet is put into nickel boat.Nickel boat is put into silica tube the appropriate rear heated sealed of logical nitrogen of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature, at 200 DEG C, after reaction 10h, is taken out silica tube cooling, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 3.5%.
Embodiment 12
The technical process that the present embodiment is prepared fluorinated graphene by Graphene is as follows:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%.
(2) prepare graphene oxide as described in Example 10.
(3) prepare Graphene as described in Example 10.
(4) fluorinated graphene: prepare fluorinated graphene by solid phase method.Its concrete steps are: process is boiled to 3h in boiling water, polyvinylidene difluoride (PVDF) after oven dry according to a certain percentage (polyvinylidene difluoride (PVDF): Graphene=50:1) mixes in organic solvent, then put into baking oven about 150 DEG C oven dry, and then compressing tablet is put into nickel boat.Nickel boat is put into silica tube the appropriate rear heated sealed of logical nitrogen of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature, at 500 DEG C, after reaction 4h, is taken out silica tube cooling, can obtain fluorinated graphene.
Can show that by table 1 mass percent of F is 4.5%.
The rare F content of table 1 fluorographite
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| F content | 30% | 28.6% | 18.4% | 25.2% | 7.5% | 0.5% | 21% | 15% | 23% | 2.8% | 3.5% | 4.5% |
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (3)
1. a preparation method for fluorinated graphene, is characterized in that, comprises the steps:
Graphite is provided;
Use described graphite-made for graphene oxide;
Described in liquid-phase reduction, graphene oxide makes Graphene;
Graphene reacts and makes fluorinated graphene with fluorine-containing material; It is cooling after described Graphene and fluorochemicals are processed 1～10h taking mass ratio as 1:1～1:100 at 200～1000 DEG C that described Graphene reacts with fluorine-containing material, and water and washing with alcohol, dry, obtain described fluorinated graphene successively;
The step that described in liquid-phase reduction, graphene oxide makes Graphene comprises:
Described graphene oxide is mixed with deionized water and be dispersed into suspension liquid;
In described suspension liquid, add reductive agent, 90～100 DEG C of thermal reduction 24～28h obtain Graphene suspension liquid;
After filtering, described Graphene suspension liquid collects filter residue, and dry after water, methanol wash successively, obtain described Graphene;
Described fluorochemicals is at least one in Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and Sodium Silicofluoride.
2. the preparation method of fluorinated graphene as claimed in claim 1, is characterized in that, uses described graphite-made to comprise for the step of graphene oxide:
Described graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES are joined according to mass ratio 2:1:1 in the vitriol oil of 75～95 DEG C, naturally cooling after stirring, washing, to dry after neutral, obtains pretreated mixture;
Described pretreated mixture and potassium permanganate are joined to temperature lower than in the vitriol oil of 20 DEG C, and then oil bath 1.5～2.5h at 30～40 DEG C, adds deionized water, adds hydrogen peroxide reaction after 15min, suction filtration, collection solid;
Described solid washs with dilute hydrochloric acid, dry, obtains described graphene oxide.
3. the preparation method of fluorinated graphene material as claimed in claim 1, is characterized in that, described reductive agent is hydrazine hydrate.
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| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
| CN103086374B (en) * | 2013-02-22 | 2014-07-23 | 杭州格蓝丰纳米科技有限公司 | Method for preparing graphene fluoride by atomic layer deposition device |
| CN104944402B (en) * | 2014-03-24 | 2017-04-26 | 中国科学院兰州化学物理研究所 | Method for quickly and efficiently preparing adjustable-fluorine-content fluoridized graphene |
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| CN105271199A (en) * | 2015-11-05 | 2016-01-27 | 湖北卓熙氟化股份有限公司 | Preparation method of fluorinated graphene |
| CN105621399A (en) * | 2015-12-25 | 2016-06-01 | 山东重山光电材料股份有限公司 | Method for preparing high-purity fluorinated graphene by taking nitrogen trifluoride as fluorine source |
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| CN108927191B (en) * | 2017-05-22 | 2021-05-28 | 天津大学 | Fluorine-containing graphite phase nitrogen carbide photocatalyst and preparation method thereof |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
| CN107501819B (en) * | 2017-09-15 | 2020-01-07 | 中国南方电网有限责任公司超高压输电公司贵阳局 | Modified polytetrafluoroethylene resin |
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| CN110877910B (en) * | 2018-09-06 | 2022-04-05 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN110877906B (en) * | 2018-09-06 | 2022-06-24 | 天津大学 | Preparation method of fluorine-doped graphene |
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